Process for breaking petroleum emulsions



2,695,889 Patented Nov. 30, 1954 fie PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application September 19, 1952, Serial No. 310,553

23 Claims. (Cl. 252-344) This invention relates to processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

The present invention is a continuation-in-part of my co-pending applications, Serial Nos. 288,744, filed May 19, 1952, 296,085, filed June 27, 1952, and 301,805, filed July 30, 1952.

My invention provides an economical and rapid process for resolving petroleum emulsions of\the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft Waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removini impurities, particularly inorganic salts, from pipeline oi The demulsifying agents employed in the present demulsifying process are the products obtained by the process of first condensing (a) An oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, lowstage phenol-aldehyde resin of the type described hereinafter in Part 1.

(b) A basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and

(c) Formaldehyde; said condensation reaction being conducted at a temperature suificiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible. The condensation reaction is followed by an oxyalkylation step by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide to form the present demulsifying agents.

In many instances and for various purposes, particularly for the resolution of petroleum emulsions of the water-in-oil type, one may combine a comparatively large proportion of the alkylene oxide, particularly propylene oxide or a combination of propylene oxide and ethylene oxide, with a comparatively small proportion of the resin condensate. In some instances the ratio by weight has been as high as 50-to-1, i. e., the ultimate product of reaction contained approximately 2% of resin condensate and approximately 98% of alkylene oxide.

This invention in a more limited aspect as far as the reactants are concerned which are subjected to oxyalkylation are certain amine-modified thermoplastic phenolaldehyde resins. Such amine-modified resins are described in the aforementioned co-pending applications and much that is said herein is identical with the text of said aforementioned co-pending applications; however, some detail is omitted since the art is aware of these resins through my mentioned copending applications, e. g., S. N. 296,085. For purpose of simplicity the invention, purely from a standpoint of the resin condensate involved, may be exemplified by an idealized formula as follows:

R R n R in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and It generally is a small Whole number varying from 1 t0 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the 'above structure is derived from a nonhydroxylated basic polyamine and usually a strongly basic polyamine having at least one secondary amino radical and free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and may be indicated thus:

RI HN/ in which R represents any appropriate hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical, etc., free from hydroxyl radicals, with the proviso that at least one occurrence of R contains an amino radical which is not part of a primary amino radical or part of a substituted imidazoline radical or part of a substituted tetrahydropyrimidine radical.

Actually, what has been depicted in the formula immediately above is only an over-simplified exemplification of that part of the polyamine which has the reactive secondary amino group. Actually, a more complete illustration is obtained by reference to substituted polyalkylene amines of the following structure:

in which R has its prior significance, R" represents a hydrogen atom or radical R, D is a hydrogen atom or an alkyl group, n represents the numerals 1 to 10, and x represents a small whole number varying from 1 to 7 but generally from 1 to 3, with the proviso that the other previously stated requirements are met. See U. S. Patent No. 2,250,176, dated July 22, 1941, to Blair.

See also U. S. Patent No. 2,362,464, dated November 14, 1944, to Britton et al., which describes alkylene diarnine and polymethylene diamines having the formula where R represents an alkyl, alkenyl, cycloalkyl, or aralkyl radical, and n represents a comparatively small integer such as 1 to 8.

A further limitation in light of the required basicity is that the secondary amino radical shall not be directly joined to an aryl radical or acyl radical or some other negative radical. Needless to say, what has been stated above in regard to the groups attached to nitrogen is not intended to exclude an oxygen-interrupted linkage or a ring linkage as in the instance of compounds obtained by converting an N-aminoalkylmorpholine of the formula wherein n is a whole number from 2 to 12 inclusive, and the nitrogen atoms are separated by at least two carbon atoms, into a secondary amine by means of an alkylating agent such as dimethyl sulfate, benzyl chloride, an alkyl ,3 bromide, an. ester of a sulfonic acid, etc., so as to yield a compound such as CHZCH2 N-onnh-n CH2-CH2 The introduction of twosuch polyamine radicals into a comparatively .smalLresin molecule for instance, one having 3 to;6.;phenolic,nuclebasspccified,talters the resultant product in a number of;ways. In the firstplace, a basic nitrogen atom, of course adds a hydrophile eifect; in the second place, dependingpn the size of the radical R, there maybe a counterbalancing hydrophobe efiect or one in whichthqhydrophobe effect more-than counterbalances the hydr ophile eifect ofthe nitrogen Q .Final1y..-' htca e Whe e nt nsicn c more oxygen atoms anotherwetfect is introduced, particularly another hydrophile eifect A y -I am not aware ,that it has been previously suggested d to modify. by oxyalkylation rthe resin condensates of the kind described herein andin. my,.copending application S. ISL-296,085 The. condensation product obtained according to the presentinvention is heat stable and, in fact, oneof its outstanding qualities is thatitpan-be subificted tooxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, ;i. e.,- presence of an alkaline catalyst, for example, but in any event at a temperature above 100 C. without becoming an insoluble mass. 11

Any reference, as in thehereto appended claims, to the procedure employed in the process is not intended to limitthe method or orcler'ain which-the reactants are added, commingled orreacted-.,;.-The procedure has-been referred to as a condensation process for obvious reasons. 35 Aspointed out elsewhere it is my preference to dissolve the: resin in a suitable solvent; add. the amine,..and :then add .the formaldehyde as .a.-37%L-solution. ;..However, all three reactants can be added in-.any-order.- I am-inclined to believe that-in the presence of a basic catalyst, 40 such as the amine, employed, that the-formaldehyde produces methylol groupsattached :to the phenolic nuclei which, in turn, react with the amine. It would be ima l; f u e; htl a msld hy s ai w th' the amine spas to introduce a, methylolgroup. attached-; to nitrogen which, in turn, would react with the ;r esirlincleculea Also, it would be immaterial ifsboth typescf compounds were ,formedwhichreacted with each other with theevolution vof a ,mole, offormaldehyde,available for further reaction .Eurtherrnore, a .reacti onacquld. take in which R"O is the radicalpt alkylene oxide, such as the ethoxy, propoxy or similar radicals derived from gly cide ethylene oxide,-propylene oxide, or thelike' and n" is a numbervarying from l to 60, with the proviso that one need not oxyalkylateall theavailablc-phenolic hydroxyl radicals. I n other words, one need only convert two phenolic hydroxyl radicals per resin molecule.

ae'sgssa 4 Statechanother:-way nkcan"be-zeroes well asa. .whole number subject to what has been said immediately preceding, all of which will be considered in greater detail subsequently.

Actually, What has beensaid previously may not be as complete an idealized presentation as is desirable due to anotherfactor which may. be involved. .Thefactoris this: Although the polyaminemi's nondiydroxylated and may have atertiary amine gr oup which is not susceptibleto oxyalkylatiom-it mayahave more than one secondary amino group as, for example, in the case of tetraethylene pentamine. Such group may or may not be susceptible to oxyalkylation under theconditions descri ed, for reasons which areobscure. Br iefiy sta'ted, .oxyalkylation seems to proceed readily at terminal secondary amino groups but less rapidly-and sometimeshardlyat all when the same group appears in the center of a large molecule.

In.,,the. instant situation uthere are-,phenolic.,hydroxyls available which are readily susceptible ,to oxyalk'ylation.

Assume for the mornent,. that the nonhydroxylate'd, amine contains a plurality of secondary amino groups a'ridthat one or more may be susceptible to,.oxyalkylation. If so,

the condensatescanbev dep1cted ..more satisfactorily in the following manner by first referring. to, the. resin condensate and then to the oxyalkylated derivative;

(HN),.-R

in which the-characters, hays theirpreyious significance, and n! is the' integ'er 0 or a small whole, number, with the proviso that in. each, terminal. amino radical there must be at least onelabile. hydrogen atorriattached to a nitrogen atom as part of a secondaryamine residue,

Thus, one can shlow it s at least theoretically possible and to some extent probable, that oxyethylation. does take place in reactions of the kind herein described, not only at the phenolichydroxyl. but, also atone, or. more of the available segondary arninogroups ,whenthey appear.

This can be depicted in the following manner:

R"o wa (l v'mi n R I o R' R' OjJQH t;- H N R in. which, for. simplicityihe formula just shown previously has been;limited to, thesspecific. instance .wheretlier .is one oxyalkylation-susceptible secondary arr'iiiioradical as part of the polyamine residue. In. the-above formula R"O is the. radical. of an alkylenecoxide such .as. the ethoxygpropoxy .or similar radicals derivedtfr'orn glycide ethylene.oxide,=.propylene oxide, or. the .like, and n. is anumber varyingfroni lto .60, with the proviso that one needanotoxyalkylate .all' the available phenolic hydroxyl radicals or all. the available amino hydrogenatoms to, the extent they: are; present... In otherwords, one need convert only. two labile hydrogen radic'alsper condensate. Itis;immaterial whether thelabile hydrogen atoms be attached to oxygen or nitrogen;..

As fanastheuse o'fthe-herein describediultimate prod ducts goesfor purpose of resolution of petroleum. emulsionsof the water-in-oil...type, I particularly prefer to use those .whichas such merely as a result of oxyalkylation alone,wor in the forr'n of the .freenbase or hydrate,

i..e., combination .with water or particularly, in the form-- of a low inolaLorganic acidsuch as the acetateor hydroxy acetate, have sufficiently hydrophile: character to at.least meetthe. test set forth in the U. S. Patent Noi.2,499.,368, dated March-.7, 1950, to .De .Groote etral. ..In. someiinstances oxyalkylation is the controlling factor rather than the basic .nitrogenatoms' present regardless of theirsti'uctune-or combination... Insaid patentsuchtest for emulsification using a. water-insoluble. solvent, generally xylene, is described as an index of surface activity.

in the. present instance the vari'ous oxyalkylated condensationproducts as :such' -orin t e .form ofthe vfree baseonin the form of the acetate, 'ri1 ay not necessarily be xylene soluble although-they are-in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a Water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Reference is again made to U. S. Patent 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said immediately aforementioned patent the following test appears:

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called subsurface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 5050 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-in-water type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a water-in-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water. If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 /2 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufliciently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surface-active characteristics in the products used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent water-insoluble solvent may mask the point at which a solventfree product on mere dilution in a test tube exhibits selfemulsification. For this reason, if it is desirable to determine the approximate point where self-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employa xylenesolution; Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

Having described the invention briefly and not neces-. sarily in its most complete aspect, the text immediately following will be a more complete description with specific reference to reagents and the method of manufacture.

For convenience the subsequent text will be divided into five parts:

Part 1 is concerned with the general structure of the amine-modified resin condensates and also the resin itself, which is used as a raw material;

Part 2 is concerned with appropriate basic secondary polyamines free from a hydroxyl radical which may be employed in the preparation of the herein described amine-modified resins or condensates;

Part 3 is concerned with the condensation reactions involving the resin, the amine, and formaldehyde to produce the specific products or compounds;

Part 4 is concerned with the oxyalkylation of the products described in Part 3, preceding; and

Part 5 is concerned with the use of the oxyalkylated amine-modified resins obtained in Part 4, preceding, for use in the resolution of emulsions of the water-in-oil type;

In the subsequent text, Parts 1, 2 and 3 appear in substantially the same form as in the text of the aforementioned co-pending applications, Serial Nos. 288,744, filed May 19, 1952, 296,085, filed June 27, 1952, and 301,805, filed July 30, 1952. Furthermore, Part 4 is essentially the same as Part 4 in the last aforementioned co-pending application, i. e., Serial No. 301,805, filed July 30, 1952.

PART 1 It is well known that one can readily purchase on the open market, or prepare fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH OH OH To--[ To H H I; R n R In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl, or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance para-phenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as ben- Zene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethylglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. The phenol aldewhich R- is an aliphatic hydrocarbon radical having at least 4 carbon atoms and notmore than 24 carbon atoms and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moresjof formaldehyde and two moles of a basic nonhydroxylat'ed secondary polyamine as specified, following the same idealized oversimplification previously referred to, the resultant product might be ill'us trafd thus:

The basic polyamine may be designated thus:

:5. structure sujch as a substituted polyalkyleneamine of in which. the various characters have the same significance as in initial presentation of this formula, then one becomes involved in added difficulties in presenting an overall picture. Thus, for sake of simplicity, the polyamine will be depicted as subject to the limitation and explanation previously noted.

In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

R1 R1 H N-C-N H R1 B1 on on on R a H H 11 Cl Cl EL HJ H \R, R R n R As' has been pointed outpreviously, as far as the resin unit goes one can use" a mole of aldehyde other than formaldehyde, suchas acetaldehyde', propionaldehyde or butyraldehyde. T he resin unit may be exemplified this:

in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appearsto be described best' in terms of the method of manufacture.

As previously stated the preparationof resins-, the kind herein employed as" reactants, is well known. Se'e previously mentioned U. S. Patent 2,499,368. Resinscan be made using an acidcata'lyst or basic catalyst or a catalyst having neither ac'd nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words,- if prepared by using a strong; acid as a catalyst, such strong acid should be neutralized. Similarly if a strong base is used as a; catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount rfiay be as small as a 200th or a percent and as much as a few IOthS of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the nidst desirable procedure in practically ever case is to have the resin neutral.

In reparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trirn'ei and pe'ntanier P'rS Iit. Thil'S, the IhOleCtilr' Weight may be such that it cone ponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I Moi. wt. R R igg n of resin molecule Phenyl Para. Formaldehyde. 3. 5 992. 5 Tertiary bntyl do. do 3.5 882. 5 Secondary butyL 3. 5 882. 5 Cyclohexyl 3. 5 1, 025. 5 Tertiary amyL... 3. 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary amyl.

7a a Propyl 3. 5 805. 5 8a Tertiary hexyl 3. 5 1,036. 5 9a 0ctyl. 3. 5 1,190. 5 N onyl 3. 5 1, 267. 5 Decyl 3. 5 1, 344. 5 Dodecy 8. 5 1, 498, 5 Tertiary butyl. 3. 5 D45. 5 Tertiary amyl... 3. 5 1, 022. 5 Nonyl (10 3. 5 1, 330. 5 Tertiary butyl... Bgtgralde- 3.5 1,071.5 Tertiary 31113 1-.-. 3. 5 l, 148. 5 Nnyls. 3. 5 1, 456. 5 Tertiary butyl. 3. 5 1, 008. 5 3. 5 1, 0 85. 5

Nonyl 3. 5 1,393. 5 Tertiary butyl. 4. 2 996. 6 Tertiary ainyL... 4. 2 l, 083. 4 Nonyl 4. 2 1, 430. 6 Tertiary butyl- 4. 8 1,094. 4 Tertiary amyl; 4. 8 1, 189. 6 Nonyl 4. 8 1, 570. 4

As has been pointed out, the amine herein employed as a reactant is a basic secondary polyamine and preferably a strongly basic secondary polyamine free from hydroxyl groups, free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl, alicyclic, arylalkyl, or heterocyclic in character.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amine group. By way of example the following formulas are included. It will be noted they include some polyamines which, instead of being obtained from ethylene dichloride, propylene dichloride, or the like, are obtained from dichloroethyl ethers in which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

Another procedure for producing suitable polyamines is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an alkylating agent of the kind described, for example, dimethylsulfate; or else a reaction which involves an alkylene oxide, such as ethylene oxide or propylene oxide, followed by the use of an alkylating agent or the comparable procedure in which a halide is used.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary aralkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylating agent, such as dimethylsulfate. In a somewhat similar procedure the secondary amine of the kind just specified can be reacted with an alkylene oxide such as ethylene oxide, propylene oxide, or the like, and then reacted with an imine followed by the final step noted above in order to convert the a secondary amino group.

Reactions involving the same two classes of reactants previously described, i. e., a secondary amine plus an imine plus an alkylating agent, or a secondary amine plus an alkylene oxide plus an imine plus an alkylating agent, can be applied to another class of primary amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula:

in which X is a small whole number having a value of l or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number 0 to 1, with the proviso that the sum of m plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514, dated July 27, 1943 to Hester, and 2,355,337, dated August 8, 1944,

primary amino group into to Spence. The latter patent describes typical haloalkyl ethers such as OHaOOzHrCl CHz-CH:

Hz; H-CHzOCsHrOCzH4B1 021150 021110 021140 0211 0 C2H4C1 Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typefied by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplified by CHsOCHzCHzCHz CHzCI-IzCHz 2NH Other somewhat similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gammaphenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517 and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as C H: H

NpropyleneNpropyleneN In the first of the two above formulas if the reaction involves a terminalamino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with. the. methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again thatone. could obtain two dilferent structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondarv amino group. If there are two points of' reactivity towards formaldehyde as illustrated by the. above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point; Indeed, there are well known suitable polyamine reactions where a large variety of compounds might be obtained due to such multiplicity of reactive radicals. This can be illustrated by the following formula:

Table II.

PART 3 The products obtained by the: herein described proc esses represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure hereinemployed is comparable, ina general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated froma resin, or inthe manufacture of a phenolamine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heat-reactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase-system, and since temperatures up to 150 C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. This procedure is noted in my copending application S. N. 296,085 and further description of certain details is unnecessary.

Needless to say, as far as the ratio of reactants goes I have invariably employed approximately one mole of the resin based on the molecular Weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances I have added a trace of caustic as an added catalyst but have found no particular advantage in; this. In other cases I have 12 used a slight excess of formaldehyde and, again, have not found any'particular. advantage -in this. In other cases I have used a slight excess of amine and, again, have not found any particular advantage in so-doing.

Whenever feasible I have checked the completenessof reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly.

in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any'is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed-for the preparation of the hereln described condensation products. The

illustration.

following example will serve by way'of Example 1 b identified previously as Example 2a. from a paratertiary butyl phenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei as the value for n which excludes the two external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6voverall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with a somewhat lesser weight of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was. then adjusted to approximately 30 to 35 C. and 176 grams of symmetrical dimethylethylene diamine added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular instance the formaldehyde used was a 30% solution and 200 grams were employed which were added in a little short of 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 46 C. for about 19 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within approximately two to three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was. set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 152 C. or slightly higher. The mass was kept at this higher temperature for three to four hours and reaction stopped. During this time, any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat less than 30 hours. In other examples, it varied from a little over 20 hours up to 36 hours. The time can be reduced by cuttiugvthe low temperature period to approximately 3 to 6'hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature. (30 to 40 C.). for a period of several hours. ployed until the odor of formaldehyde disappeared; After the odor offormaldehyde disappeared the phaseseparating trap was employed. to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken.

Then refluxing was em-- TABLE II Strength of Reaction Reaction Resin Amt, Amine used and Solvent used and Max. distill Ex. N0. used gm. amount sigirrlnalrtllglgglig amt a on-i temp D C.

882 Amine A, 176 g.. 30%, 200 g. y 600 s 20-23 26 152 480 Amine A, 88 g 30%, 100 g ylene, 450 g 20-21 24 150 633 do. do Xylene, 550 g. 20-22 28 151 441 Amine 7%, 81 Xylene, 400 g 20-28 36 144 480 do .do Xylene, 450 22-30 25 156 633 .do o Xylene, 600 21-28 32 150 882 Amine C, 204 g 30%, 200 g. do 21-23 30 145 480 Amine o, 102 g 37%, 100 g. y e 450 a 20-25 35 148 633 do d Xylene, 500 g 20-27 35 143 473 Amine D, 111 g 37%, 81 g. y e 425 s-- 20-22 31 4 ,d Xylene, 500 g 21-26 24 146 Xylene, 550 g 22-25 36 151 Xylene, 400 g 25-38 32 150 (l0 21-24 30 152 Xylene, 550 g 21-26 27 145 Xylene, 400 g -23 141 .do 22-27 29 143 Xylene, 450 g 23-25 36 149 do 21-26 32 14s Amine G, 174 Xylene, 500 g 21-23 148 d do 20-26 36 152 441 d Xylene, 440 g 21-24 32 150 595 Amine H, 282 g 37%, 81 g y 500 s 28 25 1 0 391 Amine H, 141 g.. 30%, 50 g Xylene, 350 g 21-22 23 51 As to the formulas of the above amines referred to as Amine A through Amine H, inclusive, see immediately below:

Amine A NC2H4N Amine B H H N CaHoN Amine C CH3 CHs Amine D Amine E GHQ-CH2 Amine H PART 4 propylation step insofar that two low boiling liquids are handled in each instance. What immediately follows refers to oxyethylation and it is understood that oxypropylation can be handled conveniently in exactly the same manner.

The oxyethylation procedure employed in the preparation of derivatives of the preceding intermediates has been uniformly the same, particularly in light of the fact that a continuous operating procedure was employed. In this particular procedure the autoclave was a conventional jacketed autoclave, made of stainless steel and having a capacity of approximately 25 gallons, and a working pressure of 300 pounds gauge pressure. The autoclave was equipped with the conventional devices and openings, such as the variable speed stirrer operating at speeds from 50 R. P. M. to 500 R. P. M., thermometer well and thermocouple for recorder controller; emptying outlet, pressure gauge, manual and rupture disc vent lines; charge hole for initial reactants; at least one connection for conducting the incoming alkylene oxide, such as ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cooling and heating the autoclave through the jacket. Also, I prefer coils in addition thereto, with the coils so arranged that they are suitable for heating with steam or cooling with water, and the jacket further equipped with electrical heating devices, such as are employed for hot oil or Dowtherm systems. Dowtherm, more specifically Dowtherm A, is a colorless non-corrosive liquid consisting of an eutectic mixture of diphcnyl and diphenyl oxide. Such autoclaves are, of course, in essence, small scale replicas of the usual conventional autoclave used in commercial oxyalkylating procedure.

Continuous operation, or substantially continuous operation, is achieved by the use of a separate container to hold the alkylene oxide being employed, particularly ethylene oxide. The container consists essentially of a laboratory bomb having a capacity of about 10 to 15 gallons or somewhat in excess thereof. This bomb was equipped, also, with an inlet for charging, and an outlet tube going to the bottom of the container so as to permit discharging of alkylene oxide in the liquid phase to the autoclave. Other conventional equipment consists, of course, of the rupture disc, pressure gauge, sight feed glass, thermometer, connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use and the connections between the bomb and the autoclave were flexible stainless hose or tubing so that continuous weighings could be made without breaking or making any connections. This also applied to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass, protective screens, etc.

With this particular arrangement practically all oxyethylations became uniform in that the reaction temperature could be held within a few degrees of any selected point in this particular range. In the early -.trolled.by the usual .factors, such stages where the concentration of catalyst is high the temperature was generally set for around 130 C. or thereabouts. Subsequently the temperature may be somewhat higher for instance, 135 C. to 1 40 C. Under other conditions, definitely higher temperatures may be employed, for instance 170 C. to 175 C. It will be noted by exarn'irrtion o'f subsequenfexamples that this temperature range Was satisfactory. Inany case, where the" reaction goes more slowly afhigh'erftjernperature may be used, forinstance, 140 C.,to 145,-" C., and if need be 150 C to 160 C'. Incidentally, oxypropylation takes place more slowlythan oxyethylation as a rule and for this reason I have used a temperature of approximately 130 C. to 140 C., as being particularly desirable ,for initial oxyprop'ylation, stayed within the range of 130 C..to 135 C. almost invariably during oxyprop lation. The lesser reactivity of propylene oxide compared with ethylene oxideijcan be offset by use of more ca :alyst, more vigorous agitation and perhaps a longer time was forced in by meanslof nitrogenpressure as rapidly as it was absorbed as indicated by'the pressure gauge on the autoclave. In case the reaction slowed up the temperature wasraised so as to speed up the reaction somewhat by use of extreme heati .If need be, cooling water was employed.to .controLthe temperature.

Aspreviouslypointed out i n the .c ase of xypropylation as' differentiated from oxyethylatiori,',therefwas a ,te ridency orgther'eaction to ,jslo'w. up" as the, temperature dropped much.below. thefsele'ctedpoint 'ofjre "tiomllfor instance, 135 C.' "In this ins'tanc'e,the"technique em- .ployedyasthe same .as before, .that is,, ei'therfcooling ,water .cut .,down 'or fs't'arriw'as employed, oiflthe a' d dit' flpi'op'ylene "dxidespeeded up, orfele'ctric h at used in ,additi'ori'to 'the steam in "order that" the reac on proceeded at, or near,ithe .selectedte peratures'TtoYbe m n a "-Inverfsely, ,if the reactionproceededtoo fast regardless .ofg'th'e, particular'i ,alkylene] ,oxide,; the air' 'cpi nt of reactant ,l, being.,ad de1d, [suchfas ethylene ,oxide 'wa'scu't Qw or electricalil eat,wrsfjctitibffiidi' st'arh was reduc rfif ','need .b'e, .co oling water was" ruii through bpth the jacket ,a d the cooling coil. All these operations, of course, are d'ependinglonthe re quiredn ,'gaug e"s, .ch'eck valves, has eegnppqimediout, is conventignal, an,d,'as' 'far'a's1I 'am aware can'jbe', ru n s eapy at least'ftwo" .firiilsljvvlio s ecialize inijthe manufacture of,']th i's;kindof equipment. Attention is: di'rected'to the. fact ,thatIthe use- ,o glycide .rec ui res extreme .caution." c any., scale .j:' .tl 1er than'small laboratoryor se ipilotj lant .operations."1Rure1y from .the' 'standpoint of safety; jinfthe 1h" ttgungef glycide, atteritionlis ,direc'ted'. toQthe. follow- :.ing: (a )I If prepared from glycerol .IuctrochlOrQhYdtin,

mber loffconyentiohal ijthis product should .pej mpa auveiy ,pur'e; minis ,glycidejtselfshould be asipure'as possible as the effect ofaimpurlities jis.difficult to evaluate; (a) the glycide should be introduced carefully", and precaution [should taken that it reacts as promptly as introduced, iI'feL,

that,. n,o excess of, glycide isv allowed:to',acctiniulate; (d)

,all necessary precautions, should be} talren" ,t'hatj 'glycide canno p l mg iz rs l S (*1) flu t' th high lb in poiiit,of. glycide one. can readil'yfem ploy" a. typical eparatableglassresin pot as described: in U'. .S'.'. Pat'en :No. 239.9370, dated ,March 7, 1950, arrd by numerouslaboratory supply. houses. Ifsuch ar ngementv is used to prepare laboratory scale duplications, then "care shouldgbe taken that theheatingrnantle can .be removed rapidly so as toallow for cooling; or better stiIL through an added opening ,at the top, ,the glass resin pot ,or comparable vessel should, be equipped with astainless ,steel. coolingcoil so that the potpan; e cooled mor .-rapi y ha me remov -0 mantl 1 1 er tw- ,less steel coilis introduced it means Stirrerofthepaddle .typeis changed into the centrifugal. -.type which causes, the;; fiuids or. reactants .wirling action in the center ofithepot.

th ons n Qna t i @1 :fiti .bfilt .the usetof a laboratory autoclave of thelrind previously .describedin .this part. of the text, but ,in any event, when .theinitial amountofglycide is addedto'. a suitable reactant, such as the herein described amine-modified phenolaldehyde "resin,. the .speed .of reaction .ShQlll b l a (a). the ad io 0f use. of..cooling..c oi1 so tthere, is.. no'.,.uhdue rise ,ternperand ,liave period. The ethylene oxide This :i'sj. particularly. true on offered f forfsale ature. All the foregoing is merely conventional but is i'ncluded'due to the hazard in handling glycide.

Although ethylene oxide and propylene oxide may representdess ofa hazard than glycide, yet these reactjants should be handledwith' extreme care. One suitable "procedure involves the use of prcit'iylene oxide'or butylene oxide as a solvent as Well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the appropriate resin condensate in propylene ;jo'xide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which representsthe selected resin condensate ldisjsolve'd' ih propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide'is addedto react with the liquidlmass until hydrophile properties are" obtained, if not previously present to the desired degree. .Indeed hydrophile charfacter can be reduced or balanced by use of some other "oxide Such as propyleneoxide orbutylene oxide; Since lethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreacted propylene oxide or butylene oxide which can ,be eliminated by volatilization or distillationin any suitable manner. See article entitled Ethylene oxide hazards and methods of handling,'lndustrial and Engineering Chemistry, volume 42, No. 6, June 1950, pp. 1251- 1258. Other procedures can be employed as, for example, j that described in 'U. S. Patent 1%; 2,5 86,767, dated February19,1'952,'to Wilson.

Example 10 125 C. to 130 C., and a pressure of about to or pounds, 25 pounds at" the most. In some subsequent examples pressures up to pounds were employed.

The time regulator was set so as to inject the ethylene oxide in approximately three-quarters of an hour and then continue stirring, for 15 minut es or longer, a total time of one hour. The reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction'was complete in less than an hour. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. T he amount of ethylene oxide introduced was equal'in weight to the initial condensation product, to wit, 10.82 pounds. This represented a molal ratio of 24.6 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction periodwas ,2164. A comparatively small sample, less than grams, was withdrawurnerely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequentdata, or in the data presented in tabular form in subsequent Tables 3 and 4.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations I have Withdrawn a substantial portion at the euclof each step and continued oxyalkylation on a partial residual sample. This 'was not the'case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 20 This example simply illustrates ,the further oxyalkylar ion 'ofqExampl 1c. prece n P ev -s a d, the,oXyfl ylatio l- USQQP'FiD co oun to E a ;p e 1 ,..present, at th be inn n o t sta w Obviously-the, same. at the n tof the P io s a a p .l'c'), to.w Poun Th a oun id jii ssn imt ei it tstep w s 1Q-82r und the amount-pira lyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 10.82 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 21.64 pounds and the molal ratio of ethylene oxide to resin condensate was 49.2 to 1. The theoretical molecular wight was 3246.

The maximum temperature during the operation was 125 C. to 130 C. The maximum pressure was in the range of 15 to 25 pounds. The time period was one and three-quarter hours.

Example 30 Example 40 The oxyethylation was continued and the amount of oxide added again was 10.82 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at the end of the reaction period was 5410. The molal ratio of oxide to condensate was 98.4 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 2 /2 hours. The reaction unquestionably began to slow up somewhat.

Example c The oxyethylation continued with the introduction of another 10.82 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 6492, and the molal ratio of oxide to resin condensate was 123 to 1. The time period, however, dropped to 2 hours. Operating temperature and pressure remained the same as in the previous example.

Example 60 The same procedure was followed as in the previous examples. The amount of oxide added was another 10.82

pounds, bringing the total oxide introduced to 64.92 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3 hours.

Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 75.74 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8656. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 4 hours.

Example 8c This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 86.56 pounds. The theoretical molecular weight was 9738. The molal ratio of oxide to resin condensate was 196.8 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 5 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a -gallon autoclave and then transferred to a -gallon autoclave. This is immaterial but happened to be a matter of convenience only. The sol- 13 vent used in all cases was xylene. finely powdered caustic soda.

Referring now to Tables Ill and IV, it will be noted that compounds 10 through 400 were obtained by the use of ethylene oxide, whereas 41c through 80c were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples 1c through 40c, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI, it is to be noted that the first column refers to Examples 10, 2c, 3c, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 41c through 80c are the counterparts of Examples 10 through 40c, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, four columns are blank, to wit, columns 4, 8, 11 and 15.

Reference is now made to Table V. It is to be noted these compounds are designated by d numbers, 10., 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the c series, for example, 360, 40c, 54c and 700. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 1c through 40c were obtained by the use of ethylene oxide, it is obvious that those obtained from 36c and 40c, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 540 and 70c obviously come from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial 0 series such as 36c, 40c, 54c, and 700, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by The catalyst used was molal ratio of ethylene oxide to 19' 2o using the second-oxide as-indicated by the previous ex tion," i.i.e'.',. no-xattempttto.selectively'add one andfthemthei planation, to wit, propylene oxide inwld through 1611, andf other,.or any other variant: 1 ethylene oxide in 17d through- 32d, inclusive. Needlessto say, one could start'withtethyleneroxide and In'examining the tablexbeginning with 1d, it=will be then usepropyleneoxid;.andrthenxgo backxtolsethylenea noted that the initial product, i. e., 360, consisted ofthe 5- oxide; or, inversely, start witlrpropylene-"oxide, thenusel reaction product involving 10.82 pounds of the resin conethylene oxide, and then: go back-rxto propylene oxide;i:or,'. densate, 16.23 pounds of ethylene oxide, 1.0- poundsof one could5use=a combination-in whic'lrsbutylen'etoxidetis-I caustic soda, and 6.0 pounds of the solvent. usedralong-.-with either one-f. the: twouoxides 'jusfl'men- It is to be noted that reference to the catalyst in Table tioned, or a combination of both of them.

V refers to the total amount of catalyst, i; e., thecatalyst- 10 The colors of the productszusuallyvary'fromi'areddish present from the first oxyalkylation step. plus added cataambertint .to audefinitely red, .and\ amber. Tlie:reason is lyst, if any. The same is true in. regard to the solvent. primarily'that noaefiort is made :to obtain colorless-rresinsx Reference to the solvent refers to the total solvent present, initially and the resins themselves may--be:yeIIQW-,:.amber;'. i. e-., that from thefirst oxyalkylation step plus added or even dark amber. Condensation of a nitrogenous solvent, if any. 15 product invariably yields a darker product than the origi- In this series, .it will be noted that the theoretical :monalEresin' and usually-has a reddi'sh color; The. solvent lecular Weights are given: prior to :the oxyalkylation stepemployed, if xylene, adds. nothing: torthecolor but one: andiafter the oxyalkylation step, although .the'value at may use a darker colored aromatic.petroleumzsolvent.

the end of one step 'is the value atthe beginning of the Oxyalkylation generally tends to yieldilighter. colored neXt P P Obviously y Start h al 20.products and thevmore. oxide-employed the lighter the dependson the theoretical molecular weight at the end of color of theproduct. Productscanbezpreparedtin which the ini ial oxyalkylation step; i. e., oxyethyla ion for 1d theufinal'color is a lighterfamber-With a reddish tint. Such through YP PY a r 7 t r g products can be decolorized by the use of.clays,.. bleaching It'will be noted also th t under-the molal ratio the chars'; etc; As far as use.insdemulsificationiis concerned;

values of both oxides to the resinscondensateare included; 25.- some th i d trial use there is no ju tification. for' The data .given in .regard 'to the. operating::.conditions h cost f bl hi th odu t,

1s substantlally the same as before and appears .lrrTable. Generally Speaking, h amount f alkaline catalyst presentis comparatively small and it need not be re- Products resultmgfmmithese procedures may rn'oved. Since-the products per'se are alkaline due tothe iiltfll ffiiifil i fretgisasiha tas 5323:: 3 v catayst'is'somew- 'at more 1 'cu t an or mar y 1s e the Solvent may be removed by dlstfllanon and Partlcu case for the'reason that if one adds hydrochloric acid, for.

larlyvacuurn distillation. Such distillation also may remove traces or Small amounts of, uncombinedoxide, if example, ,to neutralize. the alkalinity one may partially.

present and volatile under the conditions employed neut-ralizethe basic nitrogen. radical also, The preferred Ob i l i th use f th l id d propylene procedure-1sto lgnorethepreseneeof IllCTalkalt unless itoxide int combination one needrrot firsttuso one oxide 18 ob ectionable 01 else adda StOlChlOITlGtl'lC amount 0f andthen the other, but one can mix-the two oxides .and concentrated hydrochloricacid"equal to the caustic soda thus obtain What may be termed an indifierent oxyalkylapresent;

TABLEIIIl Composition before" Compositional. end

Molal ratio to 0-s* Ethl. Propl. 0015-. Sol- Theo. Theo. 0-s* Ethl. Propl. Cata- Solresin cmlensate oxide oxide Oxyalkylation-susceptible.

TABLE IV Composition before Composition at and E Molal ratio to 95 3 o-s* Ethl. Propl. om- Sol- Theo. Theo. o-s* Ethl. Propl. Cata- Solcmdensate Ex cmpd., oxide, oxlde, lyst, vent, mol. mol. ompd., oxide, oxide, lyst, vent, lbs. lbs. lbs. lbs. lbs. Wt. wt. lbs. lbs. lbs. lbs. lbs. Ethyl Prop] oxide oxide "Oxyalkylation-susceptlble.

TABLE V Composition before Composition at end Molal ratio to 3% 0-s* Ethl. Propl. Cata- Sol- Theo. Theo. 0-s* Ethl. Prop]. Cata- Solcondensate cmpd., oxide, oxide, lyst, vent, 111 01. 1110]. ompd., oxid oxide, lyst, vent, No lbs. lbs. lbs. lbs. lbs. wt. wt. lbs. lbs. lbs. lbs. lbs. Ethyl Prom oxide oxide Oxyalkylatlon-suseeptlble.

aeuzsaew 23' 24 TABLE VI 1 TABLE TI-Continued Solubility Max. Max. Time Solubility EX NO gig? DMIZ'Q', Thiineft- EXNO' pres? hrs-I I W C5" pTSl-L S. Water Xylene Kerosene 0' S Water Xylene Kerosene 0 7 130-140: -:10 3 39:13 as I -25 2 L 130-140 5-10 2 15-25 2% 130-140 5-10. 1 3. 15-25 2 1 v 130-140 5-10 3 15-25 3-. 1130-140 5-10 3 g} 3201-. .130-1 40 5-10 4 2H5 1 5 a 1 Insolublel 8 36111013: 3&3; 15 7 2 Emulsifiable. nis rsible."

2 P 1 -25 3 In practicing th'' present processgthertreatinga or"de'-- 2025 44 mulsif-ying agent is used in theconventional way,- wellg iknown to the art; described; "for exampleyin Patent" 15-25 2 i 2,626,929; dated EIanuary 27f 19'53}' P'art"3,'- and reference 1s 1 15-25 made thereto-fora description ofconventional procedures of 'demulsifying,:including'batch;--continuous, and down 15-25 3% the-hole demulsification; the process 'essentiallyj lnv'olvmg 15-25 introducingfa small? amount ofdemnls'iiier into-al-large amsountof'ietnulsion wlth adequatemdmvrturew1thprif 15-20 1% without the: application' of:.heat,"and allowing the mix-- 15-20 2 turelostratifiy. 5:33 3 ln manyiinsta'nces the" oxyalkylated' products;herein" 15-20 23 30 spec1fije'd"as:demulsifiers can b'e"conven1ent1y used With- 15-20 outdilution'. 1 However, as =previously -'noted,- they may 158 be :diluted' asidesired with"-any-suitablzsolvent; For "1Il- 20-30 stance, by mixing J5 parts :by 'weight ofan loxyalkylated 20410 derivative; for example; the-'product oflExample wlth 59.138 15 parts-byfrweightof xylene and 10' parts by' weight-0f 20-30 3 isopr'opyl"alcohol,'- an excellent demulsifieri is obteun'edl 5 Selection of heisolventwill vary, depending upon-the Ztgg solubility characteristics of the oxyalkylated product; and 20-25 1% of course will be dictated Fin-rpa'rt'byi economic'considera' 140-25 40 tions, i. e:, cost. 7 @8132 g Asnoted above; the products-hereinidescribedvmay'be-'1 20-25 31 used'not'only in diluted form; but also may be' used 2H5 admixedwith'someotherchemical demulsifier; 5min; Z8132 3 ture which illustrates such combination-is*tlfffollbW- 30-35 2 mg: 30-35 3/2 Oxyalkylated derivative, for example, the product of 35532 i Example 50, 20%; 30-35 3 A cyclohexylamine salt of a polypropylated naphthalene 30-35 4 monosulfonic acid, 24%;

3 1 An .rammoniumesaltuofaa. polypropylatednaphthalene 15-20 2%, monosulfonic acid, 24%; 15-20 3 A sodium salt of 'oil-solublemahogany petroleum sul- 4 1 151115" 3515 12% 15-20 41 1 v 15-20 3 5 A h1gh-bo1l1ng3aroma't1c petroleum solvent, .15 15-20 Iso'pr'opyl alcohol,5%i*' v gjg 1 The;aboveproportions'are' all'jweightpercents.

5-10. 2 /3 Havingthus described my invention what I claim as 3 1 new and desireto secure by Letters Patent, isg a 3% 2f lQA'proceses for breaking petroleum emulsions of the 5-10 4 water-ili-oiljtype characterized by; subjecting theem'ulsion 0 5 to thEcHCtiOILOf ai-demuls'ifier including the product's" ob- 38 tainedzin the.process of firstfeondensing (a) an onyalkyla- 15-20 2 ti'on-susceptible, fusible; non-oxygenated organic solvent 15-20 2 5 soluble, wafer-insoluble; low-stageiphenol-aldehyde resin 12:38 i having an? averagenmolecular weight correspondin'gz-to-at .1 15.20 4 5-least13 and not over*6 phenolic nuclei-per-resin-molecule;-1 15-20 4 7 said fresin sbei'ng difunctional only "in regard ito methylolgjgg formingmeactivityysaid resin being derived by reactionbe- 20230 i twefena?difunctional=monohydric phenol andian aldehyde: 20-30 1% i h'avingnot over 8 carbon! atoms and reactive toward said 1 38:38 phenol;.;said. resi n .being formed in thei'substantial-iab- Y 20 30 g sence;of!tri-funct1onal phenols; sa1d phenol beingiof-the" 20-30 3 1 formula: 20 30 3% 0-H 20-30 1 20-'30 1 I 20-30 1% a 20-30- 3% 20-30 3 1 20-30 4 2 in; which is an aliphatic hydrocarbonr radicali-having'i 38 i4 gatleastfwi and notnmore thanr24 carbonatomsandsub- 30:35 P stituted-finzthe 2,4,6-position;':(b) abasic'inonhydroxylat- 30-35 1 1 edpg'alyamine having at least'oneis'e'conda'ry amino group 28:22 Q and having not over 32' carbon atoms in anyradical at- 30-35 3 tached to any amino nitrogen atom and yvith the :1fur-.- 3H5 4 ther proviso that the polyamine be free from any primary resinous condensation amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and formaldehyde; said cond r-sation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (0) formaldehyde; said condensation} reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the further proviso that the ratio of reactants be approximately 1,2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

3. A process for breaking petroleum emulsions of the Water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylanion-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric treactantsl I oxide} having ,not more waterrin oil't type. ch

, reactionbe con the further proviso,

27 phenol and formaldehyde; said resinlbeingi formed in the .;substantial :absence of trifunctional ,phenols; said .phenol :being of the formula inawhich Ris an aliphatic hydrocarbon radical ;.=having.at:.least 4- and not, more; than 14 carbon atomszland substituted in the 2,4,6 position; (b) avbasicgnonhydrox- 1 ylated ;polyamine. having; at least; vone secondary 1 amino .-;group .andhaVing not. over 32. carbon atoms in any. radi- Lcal attached to; anyamino; nitrogen atom, zand-.-with:l the :further proviso 1 that the apfolyamine be free from @any iprimary amino;radical,.any substituted imidazolineradil cal: and 1 any; substiuted tetrahydropyrimidine radical, and (0) formaldehyde; i.saidicondensation reaction being; con- ;ducted ata. temperature sufiiciently high toreliminatetwas terande below the pyrolytic ,point of' the reactants and: resultantsyof reaction, with the proviso:thatthecondensation reaction becconducted'so'as toproduce a significant of Lthe .resultant in -rwhich; -each of zthe v: three :have contributed; part ofthe ultimate molecule by virtue of a formaldehyde'derived methylene ibridge flconnectin'grthe amino unitrogenlzatomvof reaction with ,naresin molecule; withl'the'addedgproviso thatithezratio l:of'reactantsbe:approximately; l, 2 andl; respectively; with ithe further proviso that saidprocedure,involveitheause. .:of a: solvent; and a with' the final: proviso vthatfthe;resinous condensation product-resulting. from the process :be -heatstable -Iand t.oxyalkylation-susceptable; rfoflowed :by: an coxyalkylation step by 1 means of ;an alpha-beta .1 alkylene than 4 :carbon atomsand selectied from: the classzconsisting'of'ethylene, oxide, propylene Qoxide, ,butylenecoxide, ;glycide,.s and methylglycide'.

. 6.1-A:proeessaforibreaking;petroleum:emulsionsofathe aracterized by subjecting the: emulsion to the action of a demulsifier includinglthe;products2obtained in the process of 1' first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolformaldehyde resin having an'average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived'by reaction between 'a *difunctional monohydric "phenol, and formaldehyde; said re'sin being formed in the substa'ntialtbsence of trifunctional phenols; said phenol {being of the formula tportion in whichtR, is, analiphatic hydrocarbon radical. having .proviso v,thatathe ,polyamine be free from anyprirnary .amino radical, any substituted imidazoline radical and l,any -subs.tituted.tetrahydropyrimidine radical, and (c) formaldehyde; saidcondensation reaction being, conducted ,,at atemperature above theiboiling pointlof water and below 150 .C.,, withthe proviso that thecondensation ductedso as topro'duce a significant por- ..tion .of the fresultant in which each of the three.reactants have contributed. part ,of .the.ultirnate,,-molecule .by virtue of .a .formaldehydezderived methylene bridge connectingut-hetamino nitrogen atom of,reaction wi th a 1, resin, molecule; with theadded proviso that the, ratio of .reactants.betapproximately l',2 andv2, respectively; ,with that, said procedure involve the use .of la. solvent and with-the final proviso: that :the resinous ,condensationprod-uct resulting, from the, process' be beat- .stable: and,oxyalkylationrsusceptible;. followed, by .an' oxy- ,alkylation step byfmeans of van alpha-beta .alkylene. oxide havingr notlmore. than 4 carbonatoms and selected. from the.,class.consisting ofaethylene oxide propylene oxide,

abutylene oxide, .glycide ,and methylglycide.

7..,A process forbreaking petroleum emulsions of the in which is a para-substituted aliphatic hydrocarbon .radical having atyleast 4 and-not more-than 14 carbon aatoms'and substituted? in the 2,4,6 position; (b) a basic nonhydroxylated polyaminelhaving' at least-one secondary amino group an'd having -notover'=32 carbon atoms in any radical attaehedtoany amino-nitrogen atom and with the ffurtherproviso that the'polyamine befree from any-primary amino radical, anys'ubstituted imidazoline radical and any substituted tetrahydropyrimidineradical, and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of Water and below 150 C., with the proviso that the condensation reaction be -conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate .-rrno le euleby virtue-of; aformaldehyde-derived I methylene abridge,connectinglthe mino nitrogen atom ofreaction Withza-resin molecule; .wi th;,the. added provisotthat the ratio of reactants be approximately 1 1,2,. and .-2, respectiv'ely;-,with theifurther proviso-that said procedure inyolve themseof a}solvent;--tand With-1116' (final; provisothat the t resinous, condensation ;,product resulting from the rocessqbe heabstable and, oxyalkylatiomsusceptible;; followed byfizan oxyalkylation step tbypmeans 40f an alphabeta alkylene oxide having-mot more, than -4- carbon atoms aand selected from; thee-class consisting. of ethylene. oxide, propylenetoxid'e, :butylene oxide, glycide and metbyl- :glycide.

8. T-hemrocessuofvclaim '1. with the-proviso that-the hydrophile; properties of a the; product of the oxyalkylated .:condensation reaction :employed intheform :of a member zoftthelclass consisting; ofa) :the: anhydro 'base as is, -(=b) the freebase, and (c) the saltof' hydroxyacetic acid, in :anequal weight; of xylene are sufficient to produce an uemulsion -whensaidxylene solution is: shaken vigorously with 1to;3'volumes:of water.

9.;1Therprocess of :breaking: petroleum emulsions as derfined in zclairn 1 whereinthewoxyalkylation" step of the -manufacturing: process is limited to 'the .use ,of'both ,ethylene oxide and/propyleneoxide tin-combination.

d0; ThETPl'OCESSFDf claim 9- with the proviso that the hydrophileproperties of the' product of: the oxyalkylated ;condensation: reaction'zernployed in: thej'formrofamember "of-the :class consisting of (a) "the anhydrobase asis, b)" the free base,;and- (c): the saltof hydroxy acetic acid, in an equal 'weight of xylene are sufficient to produce "an emulsion-when said xylene solution is shaken vigorously with 1:ito-3 volumes of water.

ll.'Thewprocessoflclaini 2 with thexproviso that the hydrophile properties" of the product'of' the oxyalkylated :condensation reaction employed in the form'of' a member rof-zthe-sclass :consisting of (a) :the'anhydro base as is, (b) the'free=base,'aand'(c)the saltofhydroxy'acetic acid, inan; equal weight of xylene are sufficient to produce an emulsioniwhen saidxylene solution is shaken vigorously with 1:10 Savolurhes :of water.'

12. The process of breaking petroleum emulsions as defined in claim 2 wherein: the oxyalkylation step of the manufacturing process isxl imited to the use of both ethylene oxide and propylene; oxide in combination.

13. The process of claim 12 With the proviso that the hydrophile properties of the product of. the oxyalkylated condensation reaction employed in the form of a member ,.of..the class consisting-bf (a)-..the anhydro basev-as'ds, (vb) the..free base, .and (c) the salttof-hydroxy acetic cacid,.in,an.equal weightiof xylene, are sufficient to: produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

14. The process of claim 3 with the proviso that the hydrophile properties of the product of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

15. The process of breaking petroleum emulsions as defined in claim 3 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide to combination.

16. The process of claim 15 with the proviso that the hydrophile properties of the product of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

17. The process of claim 4 with the proviso that the hydrophile properties of the product of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are suificient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

18. The process of breaking petroleum emulsions as defined in claim 4 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

19. The process of claim 18 with the proviso that the hydrophile properties of the product of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

20. The process of claim 5 with the proviso that the hydrophile properties of the product of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution in shaken vigorously with 1 to 3 volumes of water.

21. The process of breaking petroleum emulsions as defined in claim 5 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

22. The process of claim 21 with the proviso that the hydrophile properties of the product of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

23. The process of claim 6 with the proviso that the hydrophile properties of the product of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

24. The process of breaking petroleum emulsions as defined in claim 6 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

25. The process of claim 24 with the proviso that the hydrophile properties of the product of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sulficient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

26. The process of claim 7 with the proviso that the hydrophile properties of the product of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

27. The process of breaking petroleum emulsions as defined in claim 7 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

28. The process of claim 27 with the proviso that the hydrophile properties of the product of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,031,557 Bruson Feb. 18, 1936 2,499,365 De Groote et al. Mar. 7, 1950 2,499,368 De Groote et a1 Mar. 7, 1950 2,542,011 De Groote et a1. Feb. 20, 1951 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE PRODUCTS OBTAINED IN THE PROCESS OF FIRST CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE, SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 